Non-stalling gasoline fuel compositions



- 7 v 2,920,944 NONF STALLING GASOLINE FUEL GOMPOSITIQNS Troy LQCantrell, Drexel Hill,=-l a., and John G. Peters, Audubon, 'N.J., assignors to Gulf Oil Corporation, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Application March 3, 1955 I Serial No. 492,024

3 ms to, 44- 6;)

This invention relates to' non-stallinggasoline fuel vcompositions that are aidaptedtdiinprbv the operation of internal combustion ehgines,.; under cool,, humifd atmospheric' conditions. More'riaiticitlarly, the invention relates to gasoline fuel compositions that contain a small amount, s'u'liicie'nt to reduce'th tendencies ,of'the composition to promote engine stalling in an internal com- :bustionengi'ne of the spark ignition, reciprocating type,

of a salt of'rnor'pholine and oleic acid.

.Wheii'an internal combustion engine is operated under @001, humid atmospheric conditions, using a gasoline fuel having'a relatively low 50 percent ASTM distillation point, i.e. below about235 R, excessive engine .stalling is aptto be encountered at idling'speeds during -the warnyup period, especially .where engine idling occu follow n a Period fg t o d ope at on- Engine g-stalling under such conditions has been attributed to the partial or complete blockingof the narrow air passage that exists between the carburetor throat and the carburetor throttle valve during engine idling, by ice particles and/r solid hydrocarbon hydrates that deposit u pon and adhere to the metal surfaces of the carburetor parts. "Such icing of carburetor partsoccurs as a result The aforesaid condensation and percent ASTM distillation point Excessive engine stalling is, o f course, a source of annoyanceowing to the resulting increased fuel consump- "tion, battery wear and inconvenience of frequent restartdu s t allingehar1acteristics of gasoline fuels 'be reduced sub- 'st elly, wh r e 50 pe c t A M dis l o po n vof such gasoline fuels is sufficiently low to cause a prob- It is therefore important that the inherent engine cm in th s e p t.

We have found that the stalling characteristics of gasqlineafuel compositions that normally tend to promote engine stalling due to carburetor icing are markedly improved by the incorporation therein of a minor amount ..of a salt .of morpholine and oleic acid. In one embodiment of'the invention the gasoline composition can also contain about 0.25 to about 0.75 percent by volume of the composition of a light lubricating .oil having a viscos- -ity at 100 F. of about 50 to about 500 Saybolt Universal seconds.

The anti-stalling agent included by this invention is P a polar, surface active material possessing both hydro- :sphilicand :lipophilic properties. While the invention is znot'limited'to any theory of operation, it ap ars that t l ca ure or su ace about 0.005 percent by Weight oflth 2,920,944 Patented Jan. 1 2, i960 ice by virtue of its polarity the morpholine oleate of this invention tends to orientitself upon the metalsurfaces'of the throttle valve and other critical carburetor parts contacted bythe gasoline'composition, thus forming a moisture-displacing, residual coating on said carburetor parts, which coating tends-tOIpreVent the adherence to said metal surfaces of accumulations of ice of magnitudes sufiicient to block the narrow air passages that exist in carburetors at engine idling conditions. It is also considered that the morpholine salts of this inyention may orient themselves about small individual water or ice particles, thus tending toprevent the formationof macrocrystals of ice of a size sufficientzto block carburetor air passages at engine idlingvconditions.

When morpholine oleate is utilized in gasoline compositions that contain a, small amount of a light lubricating oil the morpholine oleate,sby virtue .of its affinity for the lubricating oil, tends to attract the oil to the same critical carburetor surfacesreferrcdjtotabove and simultaneously to increase the spreading and metal Wetting characteristics of the oil, thus, promoting thevformation of an adherent oil filmon the metal surfaces of the carburetor parts. The oil film thusappears to function in similarly as the morpholine saltwitself, butthe superior metal Wetting properties imparted tq'the oil by the additive are believed toenable the oil to displace moisture from the hat itiwould not thoroughly id p acea a t. .v 7 AS nd ated. briefly above-the mate i l which s table o a d tion torawhne fuel comp in cordance with the principlesjof this invention is the addition salt of morpholine and oleic acid.

Morpholine olegte iskuseful when incorporated in ine wmp si ca o th t pe 's o in v o t tsufficient to educe the en ine sta l n characteristics thereof. g sxem e ood resh tssan b o tained with amounts q 'ab l 0-001 toahmi 0, s-perc ntbv ei o the ga in com os tion; In most inst a jor reduction in the stalling characteristics of gasoline compositions of the type disclosed herein will be obtained by the use of morpholine oleate in; mounts of at least p a i al m t r ex le sst l sheve bee ai e y v the use in gasoline of mern glihs cl ats n mounts not exceeding about 0.01 percent by weight of the comp s Thus, t e p efe red schs ntr ti n ran a cording to this inventiq l :is-about 0.905 to about 0.01 percent y We h o hs coaa sstf n order-1 obtain further improved anti-stallingbenefits with very small morpholine salt :coneentrations, it is sometimes desirable that a small amount of light lubrioating oil of the type disclosed be used in'copjunction with the morpholine salt. j v

With respect to the particular concentration ranges mentioned above, it will be appreciated that the optimum concentration of the morpholine salt can vary acc rd ng to e Severity of the atmospheric conditions encountered in the area inwhich the gasoline is used. With regard to this factor, the problem of engine stalling due to carburetor icing resulting from the ;refrigeration by evaporating gasoline of moisture condensed from the atmosphere has been observed to he significant at atmospheric temperatures of between-about 30 and 60- F., e.g., 35, 40, 45, 50 E.;, and when the relative humidity is in excess of about 65 percent, e.g., 75, 85, 95, 99 percent. The optimum concentration .of antistalling additive should be sl lflicient to efiect a substantial reduction in the stalling te gtclencies of the fuel at the atmospheric conditions of temperature and humidity which are likely to be encountered in service.

In addition to the foregoing factors, the optimum concentration of the anti-stalling additive material varies mposit a o 3 principally according to the particular gasoline employed, since the problem of engine stalling is a function of the 50 percent ASTM distillation point of the gasoline fuel.

:Greaterconcentrations of the additive combination are normally desirable with decreasing 50 percent distillation points.

Practically speaking, the; problem of engine stalling due to carburetor icing caused by rapid evaporation of gasoline occurs only in connection with gasolines having a 50 percent ASTM distillation point of not greater than about 235 F. Accordingly, this inventionrelates only to gasolines of this type. While occasional engine stalling may occur as a result of carburetor icing at severe atmospheric .conditions of temperature and humidity with gasolines having somewhat higher 50 percent ASTM distillation-points, experience has indicated that the problem does "not assume major importance ex.-

cept with gasolines of the character indicated. The problem of engine stalling due to carburetor icingis especially severe in connection with gasolines having a 50 percent ASTM distillation point of less than about 220 F. The invention is particularly useful in connection with such gasolines. The term gasoline is used herein in its conventional sense to include hydrocarbon mixtures having a 90 percent ASTM distillation point of not more than about 392 F. and a percent ASTM distillation point of not more than about 140.

. As previously indicated," the gasoline compositions of this invention are additionally benefited with respect to non-stalling characteristics by the inclusion therein of a small amount of a lubricating oil having a viscosity at 100 F. of between about 50 and about 500 Saybolt Universal seconds; for example, an oil having a viscosity of about 100 S.U.S./ 100 F. can be .used with advantage. Although highly parafiinic lubricating distillates can be used, lubricating distillates obtained from Coastal or naphthenic type crude petroleum oils are preferred because of their superior solvent properties. The lubricating oils utilized in the gasoline compositions of this invention can have been solvent-treated, acid-treated or otherwise refined prior to incorporation into the gasoline compositions of this invention. The lubricating distillates referred to are useful in the gasoline compositions of this invention in amounts of from about 0.25 to about 0.75 percent by volume of the composition, for example 0.5 volume percent. Greater amounts of the lubricating oil can be used but without appreciable further improvement in the stalling tendencies of the. gasoline composition; however, the amount of lubricating oil used should not be so great as to adversely aifect the solubility and combustion characteristics of the ultimate gasoline compositions.

The morpholine'oleate can be incorporated into the base gasoline fuel compositions in any suitable manner. Thus the oleate'can be added as such' or in the form of dispersions or solutions in solvent such'as butanol, isopropanol, ethanol, methanol, Z-butoxyethanol, diethylene glycol monobutyl ether, benzene, toluene, heptane, kerosene, gasoline, mineral oil or the like, which solvents may or may not themselves additionally contribute to the anti-stalling characteristics of the ultimate composition. In some instances'it may'even be convenient to form the morpholine oleate in situ in the gasoline composition. If desired, the morpholine oleate can be incorporated in gasoline fuel compositions in admixture with other materials designed to improve one or more properties of the gasoline, such asantioxidants, antiknock agents, ignition control additives, dehazing agents, corrosion inhibitors, dyes and the like.

Gasoline compositions of'this invention are further illustrated by the following representative specific examples.

EXAMPLE I An anti-stalling concentrate was prepared bydissolving 1 percent by weight of morpholine oleate in 99 percent by weight of an aviation grade gasoline described below in greater detail. The foregoing concentrate was incorporated in an aviation grade gasoline that had a strong tendency to promote engine stalling in an amount of 1 percent by weight of the over-all composition. The resulting gasoline composition therefore contained morpholine oleate in a concentration of 0.01 percent by weight of the composition. A typical sample of the base gasoline employed in this example had the following inspections:

Gravity, API 68.0 Sp. gr. 60/60 F 0.709 Knock rating- Motor method, octane No 81.6 Aviation lean mixture No., octane Non--- 80.2 Aviation richmixture No., octane No 87.5 TEL, mL/gal 0.49

Heat of combustion, B.t.u./lb. (net) 19,020

%, evap. at F I EXAMPLEII,

An additional gasoline composition in accordance with this invention and having reduced engine stalling char- "acteristics'is prepared by admixture of 1 percent of the anti-stalling concentrate of Example I with the same base gasoline-described in Example I, to which there has been previously added 0.5 percent by volume of an approximately 100-S.U.S./100- F. Texas lubricating distillate, a typical sample of which had the following inspections:

Gravity, 'API 24.5 Lbs./gal., 60 F. 7.55 Viscosity, SUV, sec.:

70 F. 235 100 F. 106.0 F. 63.9 210 F. 38.3 Viscosity index 16 Flash, P-M, F. 315 Flash, O.C., F. 320 Fire, 0.0., F. 355 Pour, F. 60 Color, ASTM Union 2.0 Carbon residue, Conradson, percent 0.02 Copper strip test, 212 F. '3 hr. 0

Neutralization value, ASTM D-974-51T-Total acid No. 0.05

As heretofore indicated, morpholine oleate produces of gasolines that normally tend to promote engine stalling due to carburetor icing. To illustrate the nature of the improvement obtained, in the table following there are presented illustrative results obtained with engine tests using gasoline fuel compositions prepared in accordance with this invention. In order to demonstrate more fully the unusual efiectiveness of the morpholine salt of this invention, there are also presented in the following table the results obtained with engine tests of gasoline fuel compositions containing other amine salts.

According to the test procedure followed, the fuel compositions to be testedwere fed to a standard 216 cubic inch, six cylinder, overhead valve, Chevrolet engine, drawing air through a bed of approximately 2 inch chunks (initial size) of cracked ice packed in a standard ASTM-CPR ice tower. The engine was equipped with a standard Carter Model W-il carburetor having -.a

standard Power Glide type throttle damper. The carburetor and fuel system were insulated from the engine by means of a inch thick asbestos cement board shield, inches in width, which extended the length of the manifold.

The conditions at which the engine was operated are set forth below:

Cooling water temperature, F-

In -80 Out -95 Crankcase oil temperature, F. -150 Carburetor air intake temperature 39-41 Relative humidity, percent 82-85 6 1 agents and the like can be added to the gasoline compositions of this invention, and the invention specifically includes gasoline compositions containing such additives.

Numerous additional embodiments of the invention will readily suggest themselves to those skilled in the art. Accordingly, We do not intend to be limited by the foregoing description, but rather only by the terms of the claims appended hereto. 1

We claim:

1. A gasoline motor fuel composition comprising a major amount of a hydrocarbon mixture boiling in the gasoline range, having a 50 percent ASTM distillation point of less than 220 F., and tending to promote stalling of internal combustion engines, and a minor amount, sufiicient to reduce the stalling tendencies of the composition, of a salt of morpholine and oleic acid.

2. The composition of claim *1 wherein the hydrocarbon mixture contains additionally about 0.25 to about 0.75 percent by volume of the composition of a light lubricating oil having a viscosity at 100 F. of about 50 to about 500 Saybolt Universal seconds.

3. A gasoline motor fuel composition comprising a major amount of a hydrocarbon mixture boiling in the Table Ooncentra- Engine Test: tion, Active Stalls per 5 Composition Base Fuel Additive Ingredient, Operating Percent by Cycles 1 Base Gasoline, F. 50% ASTM Distillation 5 Point (Example I Base Fuel). 2 Base G lin Morpholine Oleate of Example I 0. 01 0 3 Base Gasoline plus 0.5 Vol. Percent 100 Texas Triethanol Amine Oleate 1 0.01 5

4- Base 'omune Oleates of tern-C 1 5 Alkyl Amines 0.01 a 5 do Tallow"-alkylaminopropylamine Monooleate 0.01 5 d n Tallow"-alkylaminopropylamine Dioleate- 0. 01 5 1 Added to gasoline in form of concentrate consisting of 1 percent solution in mixture of equal volumes of toluene and isopropanol. Gasoline itself failed to dissolve 1 percent triethanol amine oleate.

From the results presented in the foregoing table it will be seen that uninhibited gasolines having a 50 percent ASTM distillation point of less than 235 F. possess poor stalling characteristics, and that such gasolines are markedly improved by incorporation therein of small amounts of morpholine oleate. Thus, comparison of the results obtained with compositions 1 and 2 demonstates the reduction in stalling characteristics obtained by the invention. Comparison of the results obtained with compositions 2, '3, 4, 5 and 6 demonstrates the marked superiority of morpholine oleate.

To the gasoline fuel compositions of the present invention there can be added one or more additional additive agents designed to improve one or more characteristics of the gasoline fuel. For example, antioxidants, anti-knock agents, ignition control additives, other deicing agents, anti-rust agents, dyes, lead scavenging References Cited in the file of this patent UNITED STATES PATENTS 2,403,619 Skinner July 9, I946 2,466,632 Borus Apr. 5, r1949 2,600,113 Jones et al. June 10, 1952 2,667,408 Kleinholz Jan. 26, 1954 2,668,522 Hickok et al. Feb. 9, 1954 2,706,677 Duncanet al. Apr. 19, 1955 2,784,067 Duncan et a1. Mar. 5, 1957 UNTTED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noo 2,920,944 January 12, 1960 Troy L. Cantrell et a1 It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, line 16, after acid" and before the period insert said minor amount being about 0. l to about 09001 per cent by weight of the composition Signed and sealed this 21st day of June 1960.

(SEAL) Attest:

KARL H AXLINE ROBERT C. WATSON Attesting ()fiicer Commissioner of Patents 

1. A GASOLINE MOTOR FUEL COMPOSITION COMPRISING A MAJOR AMOUNT OF HYDROCARBON MIXTURE BOILING IN THE GASOLINE RANGE, HAVING A 50 PERCENT ASTM DISTILLATION POINT OF LESS THAN 220*F., AND TENDING TO PROMOTE STALLING OF INTERNAL COMBUSTION ENGINES, AND A MINOR AMOUNT, SUFFICIENT TO REDUCE THE STALLING TENDENCIES OF THE COMPOSITION, OF A SALT OF MORPHOLINE AND OLEIC ACID. 